A collection of ordered-disordered Bi_(2)WO_(6)homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process,and their photocatalytic nitrogen fixation to synthesize ammonia performance wa...A collection of ordered-disordered Bi_(2)WO_(6)homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process,and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated.Results showed that ordered-disordered Bi_(2)WO_(6)(OD-2)obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance,with a nitrogen fixation rate of 114.92μmol·g^(-1)·h^(-1).However,its crystal counterpart,Bi_(2)WO_(6)(BWO),lacked nitrogen-fixation activity.In-situ diffuse reflectance-Fourier transform infrared technique(DR-FTIR),electrochemical tests,and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface,facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N_(2) adsorbed on the disordered structure,thereby promoting the smooth progress of the nitrogen fixation reaction.展开更多
Legume-based intercropping enhances asymbiotic biological nitrogen fixation(BNF);however,the underlying mechanisms remain unclear,including the roles of soil keystone diazotroph taxa with varying niche breadths.A fiel...Legume-based intercropping enhances asymbiotic biological nitrogen fixation(BNF);however,the underlying mechanisms remain unclear,including the roles of soil keystone diazotroph taxa with varying niche breadths.A field experiment was conducted to evaluate soil BNF variations between rhizosphere and bulk soils in peanut/cotton intercropping systems and monocultures.BNF activities were measured by nitrogen fixation rates,nitrogenase activity,and nifH gene abundance.Phylogenetic null models,co-occurrence networks,and niche breadth analysis were applied to investigate the roles of diazotrophic keystone taxa and their ecological niches.Rhizosphere soils exhibited 7.8–125.5%higher BNF potentials than bulk soils,whereas intercropping systems showed 11.6–323.0%increases over monocultures for nitrogen fixation rate,nitrogenase activity,and nifH gene abundance(all P<0.05).Diazotrophic community composition and diversity differed significantly,with Proteobacteria(excluding Alphaproteobacteria)enriched in intercropping and rhizosphere soils,while Cyanobacteria and Firmicutes were less abundant.Deterministic processes,particularly heterogeneous selection,dominated community assembly in the rhizosphere(91.9%)and intercropping soils(86.3%).The co-occurrence networks consistently revealed more complex and interconnected communities in intercropping and rhizosphere soils that were dominated by opportunistic diazotrophs(78.8–85.9%),followed by specialists(10.2–18.5%)and generalists(1.38–3.80%).Keystone taxa,including opportunists such as Azoarcus,Azohydromonas,and Steroidobacter,and generalists like Pseudomonas and Azotobacter,correlated positively with microbial biomass carbon and nitrate nitrogen,contributing to enhanced BNF.Peanut/cotton intercropping enhances BNF by selectively enriching the keystone diazotrophic taxa with varying ecological roles,particularly opportunists and generalists.Such targeted intercropping strategies can optimize BNF,improve soil fertility,and promote sustainable agricultural production.展开更多
Symbiotic nitrogen fixation in members of the Fabaceae family is highly efficient and beneficial for global agriculture,but not all species in this family form root nodules with rhizobial bacteria.Nodulation mainly oc...Symbiotic nitrogen fixation in members of the Fabaceae family is highly efficient and beneficial for global agriculture,but not all species in this family form root nodules with rhizobial bacteria.Nodulation mainly occurs in plants belonging to the Papilionoideae and Caesalpinioideae subfamilies(Tederso0 et al.,2018;van Velzen et al.,2019).Nodulation mechanisms in Fabaceae are well studied(Yang et al.,2022),and genomic comparisons of nodulating and non-nodulating host species can provide valuable insights into the evolutionary and genetic basis of this key process.展开更多
Symbiotic and asymbiotic nitrogen fixation(SNF and ANF),two forms of biological nitrogen(N)fixation,are the main pathways for external N inputs into natural terrestrial ecosystems.However,the regulatory mechanisms of ...Symbiotic and asymbiotic nitrogen fixation(SNF and ANF),two forms of biological nitrogen(N)fixation,are the main pathways for external N inputs into natural terrestrial ecosystems.However,the regulatory mechanisms of SNF and ANF,particularly in response to changing environmental conditions,remain poorly understood.Here,we investigated changes in SNF and ANF rates along two altitudinal gradients in two subtropical forests on soils with granite and slate parent materials.Our results revealed distinct patterns for SNF and ANF rates.SNF rates consistently declined with increasing altitude,whereas ANF rates initially increased at lower altitudes but declined at higher altitudes.These contrasting trends were attributed to divergent regulatory mechanisms of SNF and ANF rates.Specifically,the decrease in SNF rates was primarily driven by increased soil N availability and decreased air temperature.However,the drivers of ANF rates shifted from soil properties(e.g.,phosphorus,iron,and moisture)at lower altitudes to climatic factors(e.g.,air temperature)at higher altitudes.We also observed opposite trends of SNF and ANF between forests on granite and slate,demonstrating that lithology is an important driver of both SNF and ANF.Collectively,our findings highlight the divergent mechanisms regulating SNF and ANF in subtropical forests,which contribute to improving the mechanistic representation of biological N fixation in Earth system models.展开更多
In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal...In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal-organic framework,Ce-UiO-66.Vermiculite was treated with formic acid;thus,Ce-UiO-66 particles grew in-situ on vermiculite;then,Ce-UiO-66 particles were activated by ultraviolet irradiation.The vermiculite absorbed visible light with a narrow band gap,and transferred photogenerated electrons to the active sites on Ce-UiO-66.Moreover,the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process.Therefore,with only 45.92 wt%of Ce-UiO-66,the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455nm light irradiation(apparent quantum efficiency of 4.49%),and retained at least 96.05%performance after 7×24 h of photocatalytic reaction.This cost-reduced,efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.展开更多
The replacement of energy-intensive Haber-Bosch technique for ammonia production to mitigate global warming is increasingly emphasized.In this paper,we report the preparation of Z-scheme heterojunction nanocomposites ...The replacement of energy-intensive Haber-Bosch technique for ammonia production to mitigate global warming is increasingly emphasized.In this paper,we report the preparation of Z-scheme heterojunction nanocomposites for photocatalytic nitrogen fixation by coupling ultrathin two-dimensional g-C_(3)N_(4) nanosheets with MIL-101(Fe)using a solvothermal method.Methanol was used as a hole sacrificing reagent to strengthen the catalytic performance.The highest NH3 yield of the composites under full spectrum irradiation was 472.8μmol·g^(−1)·h^(−1),which is about 3.5 times that of MIL-101(Fe).From BET results,photocatalyst with high specific surface area has superior nitrogen fixation performance.The results of PL,EIS,UPS,and ESR show that the presence of Z-scheme heterojunction is largely able to facilitate the separation of electrons and holes.It is one reason for improving performance of nitrogen fixation.The study has provided a viable approach to construct heterojunction photocatalysts with outstanding nitrogen fixation performance.展开更多
The utilization of visible light for photocatalytic nitrogen fixation offers a sustainable and eco-friendly strategy for the production of ammonia.The present study focuses on the synthesis of a series of rare earth-d...The utilization of visible light for photocatalytic nitrogen fixation offers a sustainable and eco-friendly strategy for the production of ammonia.The present study focuses on the synthesis of a series of rare earth-doped carbon nitride composite ultraviolet-activated Ce-UiO-66 catalysts,denoted as RECNactMOF,for efficient nitrogen fixation.Rare earth doping modulates the band structure of carbon nitride,facilitating the formation of a type-I heterojunction with Ce-UiO-66 and promoting photocarrier generation at nitrogen fixation sites.Among these,Sm-doped SmCN-actMOF exhibits high visible-light absorption and efficient utilization of photocarriers,resulting in an apparent quantum efficiency(AQE)of 1.58%under 495 nm light irradiation.This study provides a pathway for enhancing the nitrogen fixation efficiency of photocatalysts through the incorporation of rare earth elements,and expanding the potential applications of rare earth materials in the field of photocatalysis.展开更多
Recent studies have shown that mucilage secretion from aerial roots is an essential feature of modern maize inbred lines,with some retaining the nitrogen-fixing capabilities of ancient landraces.To explore the genetic...Recent studies have shown that mucilage secretion from aerial roots is an essential feature of modern maize inbred lines,with some retaining the nitrogen-fixing capabilities of ancient landraces.To explore the genetic basis of nitrogen fixation in mucilage and its evolution from teosinte(Zea mays ssp.mexicana)to modern maize,we developed a recombinant inbred line(RIL)population from teosinte and cultivated it under low-nitrogen conditions.Large-scale,multi-year,and multi-environment analyses of RIL-Teo,Doubled Haploid-A(DH-A),Doubled Haploid-B(DH-B),and association populations led to the identification of 15 quantitative trait loci(QTL),68 quantitative trait nucleotides(QTN),and 59 candidate genes linked to mucilage secretion from aerial roots.Functional verification of the candidate gene ZmAco3,which is associated with mucilage secretion in aerial roots,demonstrated that deletion of this gene resulted in a reduction in mucilage secretion in aerial roots.In addition,most maize inbred lines exhibited stronger mucilage secretion from aerial roots under low-nitrogen conditions than under normal-nitrogen conditions.We categorized mucilage secretion into constitutive and low-nitrogen-inducible types.Through genotype-by-environment interaction studies,8 QTL,16 QTN,and 19 candidate genes were identified,revealing the genetic mechanisms underlying mucilage secretion under low-nitrogen conditions.These findings provide a comprehensive genetic analysis of the mucilage-secreting ability of maize aerial roots,contributing to our understanding of nitrogen fixation and offering potential avenues for enhancing nitrogen fixation in modern maize lines.This research advances knowledge of plant nutrient acquisition strategies and has implications for sustainable agricultural practices.展开更多
Ammonia is nowadays one of the most important commodities chemicals intensively produced at about 175 million tons per year,contributing to 1.8%of the global energy demand.The constantly increasing NH3 demand also par...Ammonia is nowadays one of the most important commodities chemicals intensively produced at about 175 million tons per year,contributing to 1.8%of the global energy demand.The constantly increasing NH3 demand also paralleleds by the high CO_(2) emissions associated with its production.Therefore,decarbonizing NH3 synthesis is one of the most urgent contemporary challenges.Taking inspiration from Nature,solar-driven nitrogen fixation under mild conditions is one of the most promising yet challenging alternatives to classic methods.In this review,we focused our attention on the photocatalytic methods for the synthesis of ammonia;in particular,we concentrated on stable and recyclable heterogeneous Fe-based photocatalysts for producing NH3.Indeed,recoverable and widely abundant and low-cost iron catalysts may represent a very promising tool for future sustainable access to this largely desired chemical target.After an overview of the pioneering works on Fe-driven nitrogen photofixation,the recent strategies on the use of Fe are herein reported.Compared with pristine photocatalysts,adding Fe as dopant or composite and heterojunction highly enhances the photocatalytic performances,opening the way to sustainable and low-cost nitrogen production.展开更多
[ Objective] The study aimed to reveal the biological nitrogen fixation capacity by sugarcane from Brazil under the ecological conditions of Guangxi, and to provide reference for study on the biological nitrogen fixat...[ Objective] The study aimed to reveal the biological nitrogen fixation capacity by sugarcane from Brazil under the ecological conditions of Guangxi, and to provide reference for study on the biological nitrogen fixation capacity by sugarcane and related generalization and application. [ Method] The ^15N isotopic fertilizer was solely applied on plants of three sugarcane cultivars planted in greenhouse with no other fertilizer forms applied, meanwhile virus-free stem seedling was regarded as control, to measure their biological nitrogen fixation capacity using ^15N isotope. [ Result ] The nitrogen fixation rate of B8 from Brazil reached 26.91%, while Guitang 11 and RIC16 presented no or poor nitrogen fixation capacity. [ Conclusion] The sugarcane eultivar B8 from Brazil showed some nitrogen fixation capacity under the ecological conditions of Guangxi.展开更多
In China, the abuse of chemical nitrogen （N） fertilizer results in decreasing N use efficiency （NUE）, wasting resources and causing serious environmental problems. Cereal-legume intercropping is widely used to enh...In China, the abuse of chemical nitrogen （N） fertilizer results in decreasing N use efficiency （NUE）, wasting resources and causing serious environmental problems. Cereal-legume intercropping is widely used to enhance crop yield and improve resource use efficiency, especially in Southwest China. To optimize N utilization and increase grain yield, we conducted a two-year field experiment with single-factor randomized block designs of a maize-soybean intercropping system （IMS）. Three N rates, NN （no nitrogen application）, LN （lower N application： 270 kg N ha-1）, and CN （conventional N application： 330 kg N ha-1）, and three topdressing distances of LN （LND）, e.g., 15 cm （LND1）, 30 cm （LND2） and 45 cm （LND3） from maize rows were evaluated. At the beginning seed stage （R5）, the leghemoglobin content and nitrogenase activity of LND3 were 1.86 mg plant-1 and 0.14 mL h-1 plant-1, and those of LND1 and LND2 were increased by 31.4 and 24.5%, 6.4 and 32.9% compared with LND3, respectively. The ureide content and N accumulation of soybean organs in LND1 and LND2 were higher than those of LND3. The N uptake, NUE and N agronomy efficiency （NAE） of IMS under CN were 308.3 kg ha-1, 28.5%, and 5.7 kg grain kg-1 N, respectively; however, those of LN were significantly increased by 12.4, 72.5, and 51.6% compared with CN, respectively. The total yield in LND1 and LND2 was increased by 12.3 and 8.3% compared with CN, respectively. Those results suggested that LN with distances of 15-30 cm from the topdressing strip to the maize row was optimal in maize-soybean intercropping. Lower N input with an optimized fertilization location for IMS increased N fixation and N use efficiency without decreasing grain yield.展开更多
Ammonia synthesis via the Haber-Bosch process, which has been heralded as the most important invention of the 20 th century, consumes massive amounts of energy, around 1%–2% of the world’s annual energy...Ammonia synthesis via the Haber-Bosch process, which has been heralded as the most important invention of the 20 th century, consumes massive amounts of energy, around 1%–2% of the world’s annual energy consumption. Developing green and sustainable strategies for NH3 synthesis under ambient conditions, using renewable energy, is strongly desired, by both industrial and sci-entific researchers. Artificial photosynthesis for ammonia synthesis, which has recently attracted significant attention, directly produces NH3 from sunlight, and N2 and H2O via photocatalysis. This has been regarded as an ideal, energy-saving and environmentally-benign process for NH3 produc-tion because it can be performed under normal temperature and atmospheric pressure using re-newable solar energy. Although sustainable developments have been achieved since the pioneering work in 1977, many challenging issues（e.g., adsorption and activation of nitrogen molecules on the surface of photocatalysts under mild conditions） have still not been well solved and the photocata-lytic activities are generally low. In this miniature review, I summarize the most recent progress of photocatalytic N2 fixation for ammonia synthesis, focusing specifically on two attractive aspects for adsorption and activation of nitrogen molecules： one is engineering of oxygen vacancies, and the other is mimicking natural nitrogenase for constructing artificial systems for N2 fixation. Several representative works focusing on these aspects in artificial systems have been reported recently, and it has been demonstrated that both factors play more significant roles in photocatalytic N2 re-duction and fixation under ambient conditions. At the end of the review, I also give some remarks and perspective on the existing challenges and future directions in this field.展开更多
To reveal the intraspecific evolution of Leptospirillum ferriphilum isolates which thrived in industrial bioleaching ecosystems and acid mine drainages,genome sequences of L.ferriphilum YSK,L.ferriphilum DX and L.ferr...To reveal the intraspecific evolution of Leptospirillum ferriphilum isolates which thrived in industrial bioleaching ecosystems and acid mine drainages,genome sequences of L.ferriphilum YSK,L.ferriphilum DX and L.ferriphilum ZJ were determined to compare with complete genome of L.ferriphilum ML-04.The genome comparisons reveal that extensive intraspecific variation occurs in their genomes,and that the loss and insertion of novel gene blocks of probable phage origin may mostly contribute to heterogeneity of gene content among L.ferriphilum genomes.Surprisingly,a nif gene cluster is identified in L.ferriphilum YSK and L.ferriphilum ZJ genomes.Intensive analysis and further experiments indicate that the nif gene cluster in L.ferriphilum YSK inherits from ancestor rather than lateral gene transfer.Overall,results suggest that the population of L.ferriphilum undergoes frequent genetic recombination,resulting in many closely related genome types in recent evolution.The combinatorial processes profoundly shape their physiologies and provide the basis for adaptation to different niches.展开更多
Reducing nitrogen to ammonia with solar energy has become a wide concern when it comes to photocatalysis research.It is considered to be one of the more promising alternate options for the conventional Haber-Bosch cyc...Reducing nitrogen to ammonia with solar energy has become a wide concern when it comes to photocatalysis research.It is considered to be one of the more promising alternate options for the conventional Haber-Bosch cycle.Herein,2D g-C_(3)N_(4)composites with modifying ultrathin sheet MnO_(2-x)were prepared and used as nitrogen fixation photocatalyst.With the assistance of the nature of MnO_(2-x),the generation rate of NH_(3)reached 225 mmol g^(-1)h^(-1),which is more than twice over the rate of pristine 2D g-C_(3)N_(4)(107 mmol g^(-1)h^(-1)).The presence of ultrathin sheet MnO_(2-x)shortens the gap of the carriers to the surface of photocatalyst.Thus the speed of electron transfer gets increased.Besides,the construction of Z-scheme heterojunction boosts the separation and migration of photogenerated carriers.As a result,the nitrogen reduction reaction(NRR)performance gets enhanced.The work may provide an example of promoting the NRR performance of non-metallic compound.展开更多
At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficult...At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.展开更多
In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)an...In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.展开更多
Solar driven nitrogen(N_(2))fixation to synthesize ammonia is a potential alternative for the traditional Haber-Bosch approach to meeting industrial demand,but is largely hampered by the difficulties in the harvesting...Solar driven nitrogen(N_(2))fixation to synthesize ammonia is a potential alternative for the traditional Haber-Bosch approach to meeting industrial demand,but is largely hampered by the difficulties in the harvesting of solar energy and activating inert N_(2).In this work,hollow CeF_(3) nanospheres co-doped with activator Tm^(3+)and sensitizer Yb^(3+)(Yb^(3+):Tm^(3+):CeF_(3))were prepared by microwave hydrothermal method.The product was employed as a catalyst for photo-driven N_(2) fixation by adjusting the molar ratio of Ce^(3+):Yb^(3+):Tm^(3+).Results show that the porous hollow structure enhances the light-harvesting by physical scattering and reflection.In addition,heteroatom doping generates abundant fluorine vacancies(F_(V))which provide abundant active sites for adsorption and activation of N_(2).The sample with molar ratio of CeF_(3):Yb^(3+):Tm^(3+)at 178:20:2 demonstrates the highest utilization of solar energy attributed to the strongest upconversion capability of near-infrared(NIR)light to visible and ultraviolet(UV)light,and the NH_(4)+concentration achieves the highest value of 15.06μmol/(gcat∙h)under simulated sunlight while nearly 6.22μmol/(gcat∙h)under NIR light.Current study offers a promising and sustainable strategy for the fixation of atmospheric N_(2) using full-spectrum solar energy.展开更多
Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-...Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.展开更多
Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fix...Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.展开更多
Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution...Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.展开更多
文摘A collection of ordered-disordered Bi_(2)WO_(6)homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process,and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated.Results showed that ordered-disordered Bi_(2)WO_(6)(OD-2)obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance,with a nitrogen fixation rate of 114.92μmol·g^(-1)·h^(-1).However,its crystal counterpart,Bi_(2)WO_(6)(BWO),lacked nitrogen-fixation activity.In-situ diffuse reflectance-Fourier transform infrared technique(DR-FTIR),electrochemical tests,and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface,facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N_(2) adsorbed on the disordered structure,thereby promoting the smooth progress of the nitrogen fixation reaction.
基金financially supported by the National Natural Science Foundation of China(32301962 and 31901127)the China Postdoctoral Science Foundation(2024M752947)+2 种基金the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(GZC20232437)the State Key Laboratory of Cotton Bio-breeding and Integrated Utilization Open Fund,China(CB2023C02)the Natural Science Foundation of Henan Province,China(252300420222)。
文摘Legume-based intercropping enhances asymbiotic biological nitrogen fixation(BNF);however,the underlying mechanisms remain unclear,including the roles of soil keystone diazotroph taxa with varying niche breadths.A field experiment was conducted to evaluate soil BNF variations between rhizosphere and bulk soils in peanut/cotton intercropping systems and monocultures.BNF activities were measured by nitrogen fixation rates,nitrogenase activity,and nifH gene abundance.Phylogenetic null models,co-occurrence networks,and niche breadth analysis were applied to investigate the roles of diazotrophic keystone taxa and their ecological niches.Rhizosphere soils exhibited 7.8–125.5%higher BNF potentials than bulk soils,whereas intercropping systems showed 11.6–323.0%increases over monocultures for nitrogen fixation rate,nitrogenase activity,and nifH gene abundance(all P<0.05).Diazotrophic community composition and diversity differed significantly,with Proteobacteria(excluding Alphaproteobacteria)enriched in intercropping and rhizosphere soils,while Cyanobacteria and Firmicutes were less abundant.Deterministic processes,particularly heterogeneous selection,dominated community assembly in the rhizosphere(91.9%)and intercropping soils(86.3%).The co-occurrence networks consistently revealed more complex and interconnected communities in intercropping and rhizosphere soils that were dominated by opportunistic diazotrophs(78.8–85.9%),followed by specialists(10.2–18.5%)and generalists(1.38–3.80%).Keystone taxa,including opportunists such as Azoarcus,Azohydromonas,and Steroidobacter,and generalists like Pseudomonas and Azotobacter,correlated positively with microbial biomass carbon and nitrate nitrogen,contributing to enhanced BNF.Peanut/cotton intercropping enhances BNF by selectively enriching the keystone diazotrophic taxa with varying ecological roles,particularly opportunists and generalists.Such targeted intercropping strategies can optimize BNF,improve soil fertility,and promote sustainable agricultural production.
基金supported by the National Natural Science Foundation of China(No.32160142)Guangxi Natural Science Foundation(No.2023GXNSFDA026034)+3 种基金State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources(SKLCUSAb202302)to H.W.,the National Natural Science Foundation of China(No.32460062)to Y.L.,and 1+9 Leading the Charge with Open Competition'project of Sichuan Academy of Agricultural Sciences(1+9KJGG010)Fruit tree breeding project in Sichuan Province(2021YFYZ0023)to H.X.
文摘Symbiotic nitrogen fixation in members of the Fabaceae family is highly efficient and beneficial for global agriculture,but not all species in this family form root nodules with rhizobial bacteria.Nodulation mainly occurs in plants belonging to the Papilionoideae and Caesalpinioideae subfamilies(Tederso0 et al.,2018;van Velzen et al.,2019).Nodulation mechanisms in Fabaceae are well studied(Yang et al.,2022),and genomic comparisons of nodulating and non-nodulating host species can provide valuable insights into the evolutionary and genetic basis of this key process.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(No.2025A1515011004)the Shenzhen Science and Technology Program(No.JCYJ20220530150015035)+1 种基金the National Natural Science Foundation of China(No.42367035)the Chinese Scholarship Council(No.202306380142).
文摘Symbiotic and asymbiotic nitrogen fixation(SNF and ANF),two forms of biological nitrogen(N)fixation,are the main pathways for external N inputs into natural terrestrial ecosystems.However,the regulatory mechanisms of SNF and ANF,particularly in response to changing environmental conditions,remain poorly understood.Here,we investigated changes in SNF and ANF rates along two altitudinal gradients in two subtropical forests on soils with granite and slate parent materials.Our results revealed distinct patterns for SNF and ANF rates.SNF rates consistently declined with increasing altitude,whereas ANF rates initially increased at lower altitudes but declined at higher altitudes.These contrasting trends were attributed to divergent regulatory mechanisms of SNF and ANF rates.Specifically,the decrease in SNF rates was primarily driven by increased soil N availability and decreased air temperature.However,the drivers of ANF rates shifted from soil properties(e.g.,phosphorus,iron,and moisture)at lower altitudes to climatic factors(e.g.,air temperature)at higher altitudes.We also observed opposite trends of SNF and ANF between forests on granite and slate,demonstrating that lithology is an important driver of both SNF and ANF.Collectively,our findings highlight the divergent mechanisms regulating SNF and ANF in subtropical forests,which contribute to improving the mechanistic representation of biological N fixation in Earth system models.
基金supported by the National Natural Science Foundation of China(Nos.21978251,22102141 and U1904215)Natural Science Foundation of Jiangsu Province(No.BK20200044).
文摘In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal-organic framework,Ce-UiO-66.Vermiculite was treated with formic acid;thus,Ce-UiO-66 particles grew in-situ on vermiculite;then,Ce-UiO-66 particles were activated by ultraviolet irradiation.The vermiculite absorbed visible light with a narrow band gap,and transferred photogenerated electrons to the active sites on Ce-UiO-66.Moreover,the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process.Therefore,with only 45.92 wt%of Ce-UiO-66,the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455nm light irradiation(apparent quantum efficiency of 4.49%),and retained at least 96.05%performance after 7×24 h of photocatalytic reaction.This cost-reduced,efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.
基金financially supported by the Natural Science Foundation of China(22071018)the Natural Science Foundation of Jilin Province(20220101069JC)
文摘The replacement of energy-intensive Haber-Bosch technique for ammonia production to mitigate global warming is increasingly emphasized.In this paper,we report the preparation of Z-scheme heterojunction nanocomposites for photocatalytic nitrogen fixation by coupling ultrathin two-dimensional g-C_(3)N_(4) nanosheets with MIL-101(Fe)using a solvothermal method.Methanol was used as a hole sacrificing reagent to strengthen the catalytic performance.The highest NH3 yield of the composites under full spectrum irradiation was 472.8μmol·g^(−1)·h^(−1),which is about 3.5 times that of MIL-101(Fe).From BET results,photocatalyst with high specific surface area has superior nitrogen fixation performance.The results of PL,EIS,UPS,and ESR show that the presence of Z-scheme heterojunction is largely able to facilitate the separation of electrons and holes.It is one reason for improving performance of nitrogen fixation.The study has provided a viable approach to construct heterojunction photocatalysts with outstanding nitrogen fixation performance.
基金Project supported by the National Natural Science Foundation of China(22102141)。
文摘The utilization of visible light for photocatalytic nitrogen fixation offers a sustainable and eco-friendly strategy for the production of ammonia.The present study focuses on the synthesis of a series of rare earth-doped carbon nitride composite ultraviolet-activated Ce-UiO-66 catalysts,denoted as RECNactMOF,for efficient nitrogen fixation.Rare earth doping modulates the band structure of carbon nitride,facilitating the formation of a type-I heterojunction with Ce-UiO-66 and promoting photocarrier generation at nitrogen fixation sites.Among these,Sm-doped SmCN-actMOF exhibits high visible-light absorption and efficient utilization of photocarriers,resulting in an apparent quantum efficiency(AQE)of 1.58%under 495 nm light irradiation.This study provides a pathway for enhancing the nitrogen fixation efficiency of photocatalysts through the incorporation of rare earth elements,and expanding the potential applications of rare earth materials in the field of photocatalysis.
基金supported by the National Natural Science Foundation of China(32401919)the Department of Science and Technology of Henan Province(242102111126).
文摘Recent studies have shown that mucilage secretion from aerial roots is an essential feature of modern maize inbred lines,with some retaining the nitrogen-fixing capabilities of ancient landraces.To explore the genetic basis of nitrogen fixation in mucilage and its evolution from teosinte(Zea mays ssp.mexicana)to modern maize,we developed a recombinant inbred line(RIL)population from teosinte and cultivated it under low-nitrogen conditions.Large-scale,multi-year,and multi-environment analyses of RIL-Teo,Doubled Haploid-A(DH-A),Doubled Haploid-B(DH-B),and association populations led to the identification of 15 quantitative trait loci(QTL),68 quantitative trait nucleotides(QTN),and 59 candidate genes linked to mucilage secretion from aerial roots.Functional verification of the candidate gene ZmAco3,which is associated with mucilage secretion in aerial roots,demonstrated that deletion of this gene resulted in a reduction in mucilage secretion in aerial roots.In addition,most maize inbred lines exhibited stronger mucilage secretion from aerial roots under low-nitrogen conditions than under normal-nitrogen conditions.We categorized mucilage secretion into constitutive and low-nitrogen-inducible types.Through genotype-by-environment interaction studies,8 QTL,16 QTN,and 19 candidate genes were identified,revealing the genetic mechanisms underlying mucilage secretion under low-nitrogen conditions.These findings provide a comprehensive genetic analysis of the mucilage-secreting ability of maize aerial roots,contributing to our understanding of nitrogen fixation and offering potential avenues for enhancing nitrogen fixation in modern maize lines.This research advances knowledge of plant nutrient acquisition strategies and has implications for sustainable agricultural practices.
基金funded by the European Union-NextGenerationEU under the Italian Ministry of University and Research(MUR)National Innovation Ecosystem grant ECS00000041-VITALITYThe University of Perugia is acknowledged for financial support to the university project“Fondo Ricerca di Ateneo,edizione 2021”and“Fondo Ricerca di Ateneo,edizione 2022”CSGI(Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase)for the support.
文摘Ammonia is nowadays one of the most important commodities chemicals intensively produced at about 175 million tons per year,contributing to 1.8%of the global energy demand.The constantly increasing NH3 demand also paralleleds by the high CO_(2) emissions associated with its production.Therefore,decarbonizing NH3 synthesis is one of the most urgent contemporary challenges.Taking inspiration from Nature,solar-driven nitrogen fixation under mild conditions is one of the most promising yet challenging alternatives to classic methods.In this review,we focused our attention on the photocatalytic methods for the synthesis of ammonia;in particular,we concentrated on stable and recyclable heterogeneous Fe-based photocatalysts for producing NH3.Indeed,recoverable and widely abundant and low-cost iron catalysts may represent a very promising tool for future sustainable access to this largely desired chemical target.After an overview of the pioneering works on Fe-driven nitrogen photofixation,the recent strategies on the use of Fe are herein reported.Compared with pristine photocatalysts,adding Fe as dopant or composite and heterojunction highly enhances the photocatalytic performances,opening the way to sustainable and low-cost nitrogen production.
基金National Natural Science Foundation of China (3026005430660085)+1 种基金Key Project of Guangxi Academy of Agricultural Sciences (2004002)Natural Science Foundation in Guangxi Zhuang Autonomous Region (0639011)~~
文摘[ Objective] The study aimed to reveal the biological nitrogen fixation capacity by sugarcane from Brazil under the ecological conditions of Guangxi, and to provide reference for study on the biological nitrogen fixation capacity by sugarcane and related generalization and application. [ Method] The ^15N isotopic fertilizer was solely applied on plants of three sugarcane cultivars planted in greenhouse with no other fertilizer forms applied, meanwhile virus-free stem seedling was regarded as control, to measure their biological nitrogen fixation capacity using ^15N isotope. [ Result ] The nitrogen fixation rate of B8 from Brazil reached 26.91%, while Guitang 11 and RIC16 presented no or poor nitrogen fixation capacity. [ Conclusion] The sugarcane eultivar B8 from Brazil showed some nitrogen fixation capacity under the ecological conditions of Guangxi.
基金supported by the National Key Research and Development Program of China (2016YFD0300202)the National Natural Science Foundation of China (31671625, 31271669)
文摘In China, the abuse of chemical nitrogen （N） fertilizer results in decreasing N use efficiency （NUE）, wasting resources and causing serious environmental problems. Cereal-legume intercropping is widely used to enhance crop yield and improve resource use efficiency, especially in Southwest China. To optimize N utilization and increase grain yield, we conducted a two-year field experiment with single-factor randomized block designs of a maize-soybean intercropping system （IMS）. Three N rates, NN （no nitrogen application）, LN （lower N application： 270 kg N ha-1）, and CN （conventional N application： 330 kg N ha-1）, and three topdressing distances of LN （LND）, e.g., 15 cm （LND1）, 30 cm （LND2） and 45 cm （LND3） from maize rows were evaluated. At the beginning seed stage （R5）, the leghemoglobin content and nitrogenase activity of LND3 were 1.86 mg plant-1 and 0.14 mL h-1 plant-1, and those of LND1 and LND2 were increased by 31.4 and 24.5%, 6.4 and 32.9% compared with LND3, respectively. The ureide content and N accumulation of soybean organs in LND1 and LND2 were higher than those of LND3. The N uptake, NUE and N agronomy efficiency （NAE） of IMS under CN were 308.3 kg ha-1, 28.5%, and 5.7 kg grain kg-1 N, respectively; however, those of LN were significantly increased by 12.4, 72.5, and 51.6% compared with CN, respectively. The total yield in LND1 and LND2 was increased by 12.3 and 8.3% compared with CN, respectively. Those results suggested that LN with distances of 15-30 cm from the topdressing strip to the maize row was optimal in maize-soybean intercropping. Lower N input with an optimized fertilization location for IMS increased N fixation and N use efficiency without decreasing grain yield.
文摘Ammonia synthesis via the Haber-Bosch process, which has been heralded as the most important invention of the 20 th century, consumes massive amounts of energy, around 1%–2% of the world’s annual energy consumption. Developing green and sustainable strategies for NH3 synthesis under ambient conditions, using renewable energy, is strongly desired, by both industrial and sci-entific researchers. Artificial photosynthesis for ammonia synthesis, which has recently attracted significant attention, directly produces NH3 from sunlight, and N2 and H2O via photocatalysis. This has been regarded as an ideal, energy-saving and environmentally-benign process for NH3 produc-tion because it can be performed under normal temperature and atmospheric pressure using re-newable solar energy. Although sustainable developments have been achieved since the pioneering work in 1977, many challenging issues（e.g., adsorption and activation of nitrogen molecules on the surface of photocatalysts under mild conditions） have still not been well solved and the photocata-lytic activities are generally low. In this miniature review, I summarize the most recent progress of photocatalytic N2 fixation for ammonia synthesis, focusing specifically on two attractive aspects for adsorption and activation of nitrogen molecules： one is engineering of oxygen vacancies, and the other is mimicking natural nitrogenase for constructing artificial systems for N2 fixation. Several representative works focusing on these aspects in artificial systems have been reported recently, and it has been demonstrated that both factors play more significant roles in photocatalytic N2 re-duction and fixation under ambient conditions. At the end of the review, I also give some remarks and perspective on the existing challenges and future directions in this field.
基金Project(2018YFC1801804)supported by the National Key R&D Program of ChinaProjects(2016JJ3146,2017JJ3160)supported by the Natural Science Foundation of Hunan Province,China。
文摘To reveal the intraspecific evolution of Leptospirillum ferriphilum isolates which thrived in industrial bioleaching ecosystems and acid mine drainages,genome sequences of L.ferriphilum YSK,L.ferriphilum DX and L.ferriphilum ZJ were determined to compare with complete genome of L.ferriphilum ML-04.The genome comparisons reveal that extensive intraspecific variation occurs in their genomes,and that the loss and insertion of novel gene blocks of probable phage origin may mostly contribute to heterogeneity of gene content among L.ferriphilum genomes.Surprisingly,a nif gene cluster is identified in L.ferriphilum YSK and L.ferriphilum ZJ genomes.Intensive analysis and further experiments indicate that the nif gene cluster in L.ferriphilum YSK inherits from ancestor rather than lateral gene transfer.Overall,results suggest that the population of L.ferriphilum undergoes frequent genetic recombination,resulting in many closely related genome types in recent evolution.The combinatorial processes profoundly shape their physiologies and provide the basis for adaptation to different niches.
基金supported by National Natural Science Foundation of China(21776118,21808090)Natural Science Foundation of Jiangsu Province(BK20190981)+3 种基金Jiangsu Fund for Distinguished Young Scientists(BK20190045)China Postdoctoral Science Foundation(2019M661765)High-tech Research Key laboratory of Zhenjiang(SS2018002)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions,the high-performance computing platform of Jiangsu University。
文摘Reducing nitrogen to ammonia with solar energy has become a wide concern when it comes to photocatalysis research.It is considered to be one of the more promising alternate options for the conventional Haber-Bosch cycle.Herein,2D g-C_(3)N_(4)composites with modifying ultrathin sheet MnO_(2-x)were prepared and used as nitrogen fixation photocatalyst.With the assistance of the nature of MnO_(2-x),the generation rate of NH_(3)reached 225 mmol g^(-1)h^(-1),which is more than twice over the rate of pristine 2D g-C_(3)N_(4)(107 mmol g^(-1)h^(-1)).The presence of ultrathin sheet MnO_(2-x)shortens the gap of the carriers to the surface of photocatalyst.Thus the speed of electron transfer gets increased.Besides,the construction of Z-scheme heterojunction boosts the separation and migration of photogenerated carriers.As a result,the nitrogen reduction reaction(NRR)performance gets enhanced.The work may provide an example of promoting the NRR performance of non-metallic compound.
基金financially supported by the National Natural Science Foundation of China(Nos.22168040 and 22162025)the Project of Science&Technology Office of Shannxi Province(No.2022JM-062)。
文摘At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.
基金financially supported by National Natural Science Foundation of China (Grant No. 22172144)Nature Science Foundation of Zhejiang Province (Grant No. LY20B030004)。
文摘In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.
基金Project supported by the National Natural Science Foundation of China (51674043,51702026)。
文摘Solar driven nitrogen(N_(2))fixation to synthesize ammonia is a potential alternative for the traditional Haber-Bosch approach to meeting industrial demand,but is largely hampered by the difficulties in the harvesting of solar energy and activating inert N_(2).In this work,hollow CeF_(3) nanospheres co-doped with activator Tm^(3+)and sensitizer Yb^(3+)(Yb^(3+):Tm^(3+):CeF_(3))were prepared by microwave hydrothermal method.The product was employed as a catalyst for photo-driven N_(2) fixation by adjusting the molar ratio of Ce^(3+):Yb^(3+):Tm^(3+).Results show that the porous hollow structure enhances the light-harvesting by physical scattering and reflection.In addition,heteroatom doping generates abundant fluorine vacancies(F_(V))which provide abundant active sites for adsorption and activation of N_(2).The sample with molar ratio of CeF_(3):Yb^(3+):Tm^(3+)at 178:20:2 demonstrates the highest utilization of solar energy attributed to the strongest upconversion capability of near-infrared(NIR)light to visible and ultraviolet(UV)light,and the NH_(4)+concentration achieves the highest value of 15.06μmol/(gcat∙h)under simulated sunlight while nearly 6.22μmol/(gcat∙h)under NIR light.Current study offers a promising and sustainable strategy for the fixation of atmospheric N_(2) using full-spectrum solar energy.
基金supported by the National Natural Science Foundation of China(22025801)and(22208190)National Postdoctoral Program for Innovative Talents(BX2021146)Shuimu Tsinghua Scholar Program(2021SM055).
文摘Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.
基金partly supported by National Natural Science Foundation of China (No. 11975061)the Technology Innovation and Application Development Project of Chongqing (No. cstc2019jscx-msxmX0041)+1 种基金the Construction Committee Project of Chongqing (No. 2018-1-3-6)the Fundamental Research Funds for the Central Universities (No. 2019CDQYDQ034)。
文摘Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.
基金supported by the National Natural Science Foundation of China(No.22108108,22205108,and No.22108106)China Postdoctoral Science Foundation No.2022M721381.
文摘Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.
